Fluorooxyphosphoranes



r n r "*1 l lo inslri salt zirfiifa eliiifi tlitt f $368,000 FLUOROOXYPHOSPHORANES Robert Arnold Braun, Newark, Del., assignor to E. i. du Pont de Nemonrs and Company, Wilmington, Del, a corporation of Delaware No Drawing. Filed Oct. 30, 1964, Ser. No. 407,895 3 Claims. (CI. 260-937) ABSTRACT OF THE DISCLOSURE Fluorooxyphosphoranes having the structure 0 o 'R|( 3--t JR1 where R and R are perfluoroalkyl radicals and R R and R are various alkyl, substituted alkyl, cyclo' alkyl, phenyl and substituted phenyl radicals.

This invention relates to novel fluoro oxyphosphoranes. It is more particularly directed to fluoro oxyphosphoranes having the following structures:

where 3,368,000 Patented Feb. 6, 1968 and In structure (1), the R and R, substituents can be joined by an alkylene bridge having the structure (CH or by such an alkylene bridge substituted with 1-3 alkyl radicals of 1 through 4 carbon atoms. I

The compounds of the invention can be prepared by reacting a trivalent organic phosphorous compound with a perfiuoro ketone according to the following equations:

40 where R -R have the same meaning as in structures (1) and (2).

The compounds of the invention are prepared by bringing stoichiometric proportions of the reactants together in a bomb. The reaction is carried out at autogenous pres-- sure at a temperature of 0200 C., preferably -150 C. This temperature is maintained for from 4 to 24 hours, preferably 8 hours.

The reaction need not be run in an inert medium, but one can use a hydrocarbon medium such as benzene or 50 hexane for better heat distribution in the bomb.

The products of these reactions are colorless crystalline .flsolids which can be purified if desired by recrystallizatibii from hydrocarbon solvents such as petroleum ether or hexane, or by sublimation under reduced pressure, The

compounds are, generally speaking, soluble in most or ganic solvents but insoluble in water.

The compounds of the invention are useful as fire and flame retardants for wood, natural fibers, paper and other ci'iinbustible substrates. Such materials can be made more 0 resistant to burning by applying a 1-l0%, by weight, solution of a compound of the invention i n p etroleum e ther or acetone and then air-drying the material.""

Preferred for the superior tire and flame retarding characteristics they confer are the compounds of structures (1) and (2) where R, and R are -CF Highly preferred for this use are the compounds of structure (1) where R; and R are CF;, and R and R are bridged.

The following examples are submitted so that the invention may be more easily understood and readily practiced. They are intended to illustrate only preferred embodiments of the invention. Those skilled in the art will no doubt compose numerous variations on the central theme, the most probable being the addition of innocuous substituents to the compounds nuclei. Though these substituertts may not be specifically disclosed, it is naturally understood that the resulting compounds are part of the basic concept and are therefore a part of the invention. 5

Example I A 5%, by weight, solution of this compound in benzene was prepared. A piece of ;-inch hardwood veneer was dipped into this solution and air dried. The wood s0 treated did not burn, even when exposed to an open flame.

The compounds listed in the following table can be similarly prepared by reacting the corresponding listed phospho reactants, in the listed amounts with hexafluoroacetone:

dimet iylono phosphite 3,868,000 5 6 Example 2 The claims are:

1. A compound selected from the group consisting Di he 1 h l h l p ny p my D osphomte (88 2 grams 03 mole) of compounds having the structures and hexafiuoroacetone (100 grams, 0.6 mole) were heated in a stainless steel bomb at 100 C. for 6 hours. The prod- (1) R g R uct (170 grams), a clear yellow oil, crystallized com- 5 a pletely on cooling and was then purified by recrystallizmg from petroleum ether. The resulting colorless crystals 0 0 had a melting point of 74-76" C. R Analysis of these crystals gave the following data: Calcd. for C H F O P: F, 36.40; P, 4.94. Found: F, R2 36.06; P, 5.01. and

This compound had the structure (2) R5 :1 CH. 15 mt s om 0 A O 0 p l/ P o 0 O RiCC-R1 mo o- :J om

CF51 CF15 where Corresponding compounds of the invention can be sim- R and R are perfiuoroalkyl radicals of 1 through 5 ilarly prepared by using the perfiuoro ketones listed in carbon atoms; the following table, in the listed amounts, for hexafluoro- R and R are selected from the group consisting of acetone: alkyl radicals of 1 through 12 carbon atoms; alkyl radicals of 1 through 12 carbon atoms substituted K t A with radicals selected from the group consisting of 6 one moum'g chlorine, bromine, cyano and alkyl of 1 through 5 carbon atoms; cycloalkyl of 5 through 7 carbon C3F7CO3F7 220.0 atoms, phenyl and phenyl substituted with radicals Perfluomheptamne selected from the group consisting of chlorine, bromine, cyano, and alkyl of 1 through 5 carbon atoms, 7 19 with the proviso that R and R; can be joined by an P rfiu r h xa alkylene bridge selected from the group consisting of (CH and (CH substituted with 1-3 alkyl Example 3 radicals of 1-4 carbon atoms;

40 and Neopentyl pheny phosphlte grams mole) i R is selected from the group consisting of alkyl radihexafluomacetone (67 grams m01e)were heated m cals of 1 through 12 carbon atoms; alkyl radicals of f stamiess steel 139mb q 8 how-Is at 9 The result 1 through 12 carbon atoms substituted with radicals mg whl'te crystailme 9 was recrysialhzed q selected from the group consisting of chlorine, broleum ether to give white needles having a melting point 45 mine and cyano; O alky1 radicals of 1 through 5 of 88-89 carbon atoms; cycloalkyl radicals of 5 through 7 car- These crystals, on analysis, gave the following data: b t henyl d phenyl substituted with radi- P g a 'zp f cals selected from the group consisting of chlorine, oun 3 bromine, cyano and alkyl of 1 through 5 carbon This compound had the structure: atoms CH3 2. A compound of claim 1 wherein R and R are on 0 on a 3. A compound of claim 1 wherein R and R are CF;, and R and R are bridged.

PO-OH2 I I No references cited. sC 1* 1 a CHARLES B. PARKER, Primaiy'Examiner.

CFS a B. BILLIAN, A. .H. SUTTO, Assistant Examiners. 

